Accelerating Effect of DMAP on CuI Catalyzed Buchwald‐Hartwig C‐N Coupling: Mechanistic Insight to the Reaction Pathway

Abstract

An efficient methodology has been developed for C−N cross‐coupling reaction between aryl halide and amine using a catalytic system comprised of CuI and N,N‐dimethyl amino pyridine (DMAP). Coupling reactions were carried out in DMSO at 120 °C in presence of 5 mol% CuI, 20 mol% DMAP and 2.5 equivalent of KOH. Addition of DMAP was found to be beneficial in accelerating the rate of reaction significantly. Both aryl iodides and aryl bromides could be successfully coupled with different primary and secondary amines to furnish the desired cross‐coupling product in high yield. A copper complex [Cu(DMAP)4I]I made by combining CuI and DMAP was found to produce superior result for the Buchwlad‐Hartwig cross coupling reaction. The use of 2 mol% of the copper complex is sufficient to produce high yield of the product.

Preparation of chiral DMAP derivatives and investigation on their enantioselective catalytic activity in benzazetidine synthesis and kinetic resolutions of alcohols

“…In many literature reports, the amination of aryl halides is promoted by palladium-based catalysts by the Buchwald-Hartwig reaction [49,50]. In this synthesis we explored the possibility to apply a Cu I catalyzed version [51,52] of the reaction. The last step of the synthesis was carried out by treatment of 7 with CuI in basic conditions.…”

Application of statistical learning and mechanistic modelling towards mapping the substrate electronic space in a Cu-catalyzed Suzuki–Miyaura coupling

“…[25][26][27] Currently, it is possible to find a recent example for almost any of the classical coupling reactions such as Heck, 28 Sonogashira, 29 Stille, 30 Hiyama, 31 and Buchwald-Hartwig. 32 The Suzuki-Miyaura reaction, one of the most representative metal-catalyzed cross-couplings, has several versions in which the typical palladium catalysts have been replaced by analogous copper complexes. [33][34][35][36][37][38][39] Recently, a Cu-catalyzed Suzuki-Miyaura coupling of highly fluorinated aryl boronate esters with aryl iodides has been reported.…”

bis‐(Aminophenyl)ferrocene ligand for palladium free CuI catalyzed Csp2−Csp cross‐coupling reaction

“…To the best of our knowledge only a few references are available for Cu catalyzed Sonogashira reaction promoted by ferrocene based ligand till date [12] Lin et al have used 1,1'bis(diphenylphosphino)ferroceneas ligand in the reaction between iodobenzene and phenylacetylene as a part of their study of copper-catalyzed cross-coupling reaction of alkynes with aryl iodides. [12] In continuation of our studies on CuI catalyzed organic transformations [35][36][37][38][39][40][41][42][43] we wish to report herein, a palladium free CuI catalyzed Sonogashira coupling reaction in presence of bis-aminophenyl-ferrocene based ligands (Scheme 1).…”